Phosphorus peroxides

Numerous sulfur and phosphorus peroxy compounds such as monopersulfuric acid (Caro s acid, la), monopersulfate (Oxone, Ib), ammonium monopersulfate Ic, tetra n-butyl-ammonium monopersulfate Id, peroxydisulfates 2a and 2b", tetra n-butylammonium peroxydisulfate 2c, symmetrical bissulfonyl peroxide 3 , acyl sulfonyl peroxide 4 , unsymmetrical sulfonyl peroxide 5 , sulfinyl peroxy intermediates 6a, sulfonyl peroxy intermediate 6b, sulfonimidoyl peroxy intermediate 7, bis(diphenyl phosphinyl) peroxide 8 , unsymmetrical phosphorus peroxide 9 and phosphoranyl peroxy intermediate 10" are known. Recently, many researchers have shown interest in the preparation and... 

Compared with peroxysulfur compounds, very few peroxyphosphorus compounds are reported. Phosphorus peroxide derivatives have been postulated as possible intermediates in certain biological transformations, although they have never been isolated in such systems . Monoperoxyphosphonic acid can be prepared in situ and applied for some common oxidation reactions ". Only one example of phosphorus peroxide, i.e. bis(phenylphosphinyl) peroxide, has been studied . It is believed that when trivalent phosphorus compounds are allowed to react with ozone and a source of singlet oxygen, phosphorus ozonides 54 are obtained (equation 89). ... 

The only symmetric phosphorus peroxide reported is bis(diphenylphosphonyl) peroxide 8. It is prepared by condensation of diphenylphosphinyl chloride with sodium peroxide (equation 94). When the same procedure was applied for substituted arenephosphinyl chlorides, no peroxide was observed. Peroxide 8 is stable at —80 °C and decomposes at room temperature. 

Since the first synthesis of the peroxyphosphoms ester 66 °, considerable efforts have been made to characterize the expanding chemistry of organophosphorus peroxy esters. Later, unsymmetrical phosphorus peroxides, such as peroxyphosphates 67 , peroxyphos-phonates 68 and peroxyphosphinates 69 , were reported. They can be prepared by the reactions of the chlorides and a tertiary carboxylic acid in the presence of base. 

Sulfur and phosphorus peroxides but without any detailed experimental evidence (equation 104) . 

Phosphorus peroxides, 1039-46 symmetrical, 1041-2 unsymmetrical, 1042-4 Photocalorimetry, ozonides, 165 Photochemistry... 

---